Integrated processes to produce gasoline blending components from light naphtha

ABSTRACT

A process for the treatment of a light naphtha feedstock that comprises normal paraffins and iso-paraffins may include separating the feedstock into a first iso-paraffin stream and a normal paraffin stream. The separating may be performed with 5 A molecular sieves, a pressure of about 1-3 bars, and a temperature of 100-260° C. A product stream may be provided by subjecting the normal paraffin stream to at least one of steam cracking, isomerizing, and aromatizing.

BACKGROUND OF INVENTION

Light naphtha, which is generally defined as a C5-C6 hydrocarbonfeedstock, originates from routine refinery processes. Light naphtha isgenerally used as a feed for steam crackers for light olefin production,and as a blending stock for gasoline production. However, light naphthais generally an undesirable gasoline blending component because of itslow octane number and high vapor pressure. Thus, the transformation oflight naphtha into value-added gasoline blending components is anongoing challenge.

The transformation of light naphtha is rendered difficult by the inertnature of carbon-carbon and carbon-hydrogen bonds, which requireelevated temperatures for processing, providing unfavorablethermodynamics, low selectivity and yields, and high cost. As refinersprocess lighter feeds, such as shale oil and condensates, the generationof light naphtha is increasing. Targets include the production ofisoalkanes, olefins, and/or aromatics from light naphtha. Thesecomponents generally provide a higher octane number and, thus, are moreuseful additives for gasoline compositions

To date, options for processing light naphtha have been limited. Typicalprocesses are depicted in FIGS. 1A-1B, which directly subject a lightnaphtha feedstock 10 to either steam cracking 110 (FIG. 1A) orisomerization 120 (FIG. 1B). The steam cracking 110 generates a crackedproduct stream 12 that mainly comprises C₂₋₄ olefins and methane, withsmaller quantities of other products. The isomerization 120, incontrast, results in an isomerized product stream 14 that consistsessentially of iso-paraffins (or “isomerate”), resulting in an increasein the research octane number (RON).

SUMMARY

This summary is provided to introduce a selection of concepts that arefurther described below in the detailed description. This summary is notintended to identify key or essential features of the claimed subjectmatter, nor is it intended to be used as an aid in limiting the scope ofthe claimed subject matter.

In one aspect, embodiments disclosed herein relate to processes fortreating a light naphtha feedstock that includes normal paraffins andiso-paraffins having 5 or 6 carbon atoms. The processes may includeseparating the feedstock into an iso-paraffin stream and a normalparaffin stream. The normal paraffin stream may be aromatized to producean aromatic stream and a non-aromatic stream, and the non-aromaticstream may be subjected to steam cracking to provide an olefinic stream.

In a further aspect, embodiments disclosed herein relate to processesfor treating a light naphtha feedstock that includes normal paraffinsand iso-paraffins having 5 or 6 carbon atoms. The processes may includeseparating the feedstock into an iso-paraffin stream and a normalparaffin stream. The separation may be performed with 5 A molecularsieves, a pressure of about 1-3 bars, and a temperature of 100-260° C. Aproduct stream may be provided by subjecting the normal paraffin streamto at least one of steam cracking, isomerizing, and aromatizing.

Other aspects and advantages of the claimed subject matter will beapparent from the following description and the appended claims.

BRIEF DESCRIPTION OF DRAWINGS

FIGS. 1A-B are schematic illustrations that depict prior art processesfor processing light naphtha.

FIG. 2 is a schematic illustration depicting a process and system of oneor more embodiments of the present disclosure.

FIG. 3 is a schematic illustration depicting a process and system of oneor more embodiments of the present disclosure.

FIG. 4 is a schematic illustration depicting a process and system of oneor more embodiments of the present disclosure.

FIG. 5 is a schematic illustration depicting a process and system of oneor more embodiments of the present disclosure.

DETAILED DESCRIPTION

Embodiments in accordance with the present disclosure generally relateto processes and systems for upgrading light naphtha to value addedproducts. Generally, embodiments in accordance with the presentdisclosure involve an initial separation step that isolatesiso-paraffins from normal paraffins. The normal paraffins may then beprocessed through one or more processes selected from the groupconsisting of steam cracking, isomerization, and aromatization.

Traditional processing of a naphtha feed stream may only use a naphthasplitter, which segregates different fractions according to boilingpoint ranges. However, as distinct hydrocarbon fractions may haveboiling points that overlap, this method is insufficient for, forinstance, separating iso-paraffins from normal paraffins. Therefore,naphtha processing is typically performed on a mixture of normal andiso-paraffins. However, the operation of a cracking unit works mostefficiently with normal hydrocarbons, and so the presence ofiso-paraffins decreases the efficiency of the cracking process. Further,if the naphtha feedstock is isomerized, the isomerization will also beless efficient as the light naphtha feedstock will already comprise asignificant isomerate fraction.

For the purposes of the present disclosure, accompanying components thatare conventionally used in light naphtha processing, such as airsupplies, catalyst hoppers, gas handling apparatus, spent catalystdischarge sub-systems, catalyst replacement sub-systems, valves,temperature sensors, electronic controllers and the like, are not shownor discussed herein for sake of simplicity. One of ordinary skill in theart would appreciate that such components may be included in theembodiments disclosed herein.

FIG. 2 depicts a process and a system of one or more embodiments of thepresent disclosure, the system comprising a separation unit 200 and acracking unit 210.

In one or more embodiments, a light naphtha feedstock 10 is fed into aseparation unit 200. The light naphtha feedstock 10 of one or moreembodiments may comprise a mixture of C5 and C6 hydrocarbons. In furtherembodiments, the light naphtha feedstock 10 may consist essentially ofC5 and C6 hydrocarbons or consist of C5 and C6 hydrocarbons. In certainembodiments the feedstock 10 may have an initial boiling point of any of10, 20, 30, 36, 40, 50, and 65° C., and a final boiling point of any of75, 78, 80, 85, 90, 95, 100, and 110° C. In one or more embodiments, thefeedstock 10 in accordance with the present disclosure may be ahydrocarbon fraction having a boiling point ranging from about 30 to 90°C. In further embodiments, the feedstock 10 in accordance with thepresent disclosure may be a hydrocarbon fraction having a boiling pointranging from about 36 to 78° C.

The light naphtha feedstock 10 of one or more embodiments may compriseat least a portion of iso-paraffins, saturated hydrocarbons with abranched-chain structure, and normal paraffins, saturated hydrocarbonswith a straight-chain structure. In one or more embodiments, thefeedstock 10 in accordance may comprise iso-paraffins in an amountranging from about 30 to 70% by weight (wt. %). In some embodiments, thefeedstock may comprise the iso-paraffins in an amount ranging from alower limit of any of 30, 40, 45, and, 50 wt. % to an upper limit of anyof 40, 45, 50, 55, 60, and 70 wt. %, where any lower limit can be usedwith any mathematically-compatible upper limit. In one or moreembodiments, the feedstock 10 in accordance may comprise normalparaffins in an amount ranging from about 30 to 70% by weight (wt. %).In some embodiments, the feedstock may comprise the normal paraffins inan amount ranging from a lower limit of any of 30, 40, 45, and, 50 wt. %to an upper limit of any of 40, 45, 50, 55, 60, and 70 wt. %, where anylower limit can be used with any mathematically-compatible upper limit.In one or more embodiments, the feedstock 10 may be sourced from one ormore of crude oil, a gas condensate, liquid coal, biofuels, andintermediary refinery processes.

The feedstock 10 of one or more embodiments may have a sulfur content of10 parts per million by weight (ppmw) or less, 5 ppmw or less, 3 ppmw orless, 1 ppmw or less, 0.5 ppmw or less, less than 0.3 ppmw, or 0.1 ppmwor less. In one or more embodiments, the feedstock 10 may have a sulfurcontent of 100 ppmw or more, 1000 ppmw or more, 5000 ppmw or more, or10000 ppmw or more.

The feedstock 10 of one or more embodiments may have a nitrogen contentof 10 ppmw or less, 5 ppmw or less, 3 ppmw or less, 1 ppmw or less, 0.5ppmw or less, less than 0.3 ppmw, or 0.1 ppmw or less.

In one or more embodiments the feedstock 10 is separated in a separationunit 200. The separation of one or more embodiments isolates theiso-paraffins of the feedstock from the normal paraffins. The separationprovides an iso-paraffin stream 20 and a normal paraffin stream 21. Inone or more embodiments, the iso-paraffin stream 20 may consistessentially of or, in some embodiments consist of, iso-paraffins. In oneor more embodiments, the normal paraffin stream 21 may consistessentially of or, in some embodiments consist of, normal paraffins.

In one or more embodiments, a molecular sieve adsorption process is usedto separate normal paraffins from iso-paraffins. In some embodiments,this separation method relies on the pore size of the molecular sieve toselectively adsorb normal paraffins due to the relatively smallermolecular diameter of normal paraffins compared to iso-paraffins. Aswould be appreciated by those having ordinary skill in the art, theadsorption step is followed by a desorption step for net recovery ofnormal paraffins. These steps may be performed cyclically orpseudocontinuously. In a pseudocontinuous process, a portion of themolecular sieves are cycled between the adsorption and desorption steps,while a remaining portion of the sieves are maintained under theseparation conditions. One of ordinary skill in the art will appreciate,with the benefit of this disclosure, that the selection of a molecularsieve is dependent upon the identity, and relative sizes, of the normaland iso-paraffins. In one or more embodiments disclosed herein, theseparation may comprise the use of a 5 A molecular sieve adsorbent.

In some embodiments, the separation step may separate straight chain C5and/or C6 paraffins from branched C5 and/or C6 paraffins. In additionalembodiments, not shown in FIG. 2, straight chain paraffins and singlybranched C6 paraffins in the isomerate reaction mixture may be separatedfrom C6 paraffins having two or more branches.

In one or more embodiments, the separation in accordance with thepresent disclosure may be performed at a pressure ranging from about 0.5to 4 bar. In some embodiments, the separation may be performed at apressure ranging from a lower limit of any of 0.5, 0.8, 1.0, 1.2, 1.5,and 1.8 bar to an upper limit of any of 2.2, 2.5, 2.8, 3.0, 3.5, and 4.0bar, where any lower limit can be used with anymathematically-compatible upper limit. In particular embodiments, theseparation in accordance with the present disclosure may be performed ata pressure ranging from about 1 to 3 bar.

In one or more embodiments, the separation 200 in accordance with thepresent disclosure may be performed at a temperature ranging from about20 to 280° C. In some embodiments, the separation may be performed at atemperature ranging from a lower limit of any of 20, 50, 95, 100, 120,140, 160, and 180° C. to an upper limit of any of 180, 200, 220, 240,260, and 280° C., where any lower limit can be used with anymathematically-compatible upper limit. In particular embodiments, theseparation in accordance with the present disclosure may be performed ata temperature ranging from about 100 to 260° C.

In one or more embodiments, after separation 200, the normal paraffinstream 21 may be fed to a steam cracking unit 210. Steam cracking is apetrochemical process in which saturated hydrocarbons, such as normalparaffins, are broken down into smaller, often unsaturated,hydrocarbons. The steam cracking process 210 detailed herein may producevarious products, including lighter alkenes (olefins) such as ethylene,propylene, and butadiene, as well as methane and aromatics such asbenzene and toluene.

In one or more embodiments, the normal paraffin stream 21 may be dilutedwith steam (not shown on FIG. 2) and then heated in an anaerobicfurnace. After the cracking temperature has been reached, the gas isquickly quenched to stop the reaction in a transfer line exchanger. Theproducts generated in the reaction, and their yield, generally depend onthe composition of the feed, on the hydrocarbon to steam ratio and onthe cracking temperature (which may be very high), and furnace residencetime (which may be very short). Generally, higher cracking temperaturesfavor the production of ethylene and benzene, whereas lower temperaturesproduce relatively higher amounts of propene, C4-hydrocarbons, andliquid products.

In one or more embodiments, the steam cracking in accordance with thepresent disclosure may be performed at a temperature ranging from about600 to 1000° C. In some embodiments, the steam cracking may be performedat a temperature ranging from a lower limit of any of 600, 700, 750,775, 800, 825, and 850° C. to an upper limit of any of 850, 875, 900,950, and 1000° C., where any lower limit can be used with anymathematically-compatible upper limit. In particular embodiments, thesteam cracking in accordance with the present disclosure may beperformed at a temperature ranging from about 700 to 900° C. Inparticular embodiments, the steam cracking in accordance with thepresent disclosure may be performed at a temperature of approximately800° C.

In one or more embodiments, the steam cracking in accordance with thepresent disclosure may be performed at a pressure ranging from about 0.8to 1.5 bar. In some embodiments, the steam cracking may be performed ata pressure ranging from a lower limit of any of 0.8, 0.9, 1.0, 1.1, and1.2 bar to an upper limit of any of 1.0, 1.1, 1.2, 1.3, 1.4, and 1.5bar, where any lower limit can be used with anymathematically-compatible upper limit. In particular embodiments, thesteam cracking in accordance with the present disclosure may beperformed at a pressure ranging of approximately 1 bar.

In one or more embodiments, the steam cracking in accordance with thepresent disclosure may be performed at a steam to hydrocarbon ratioranging from about 0.1:1 to 0.8:1 by weight. In some embodiments, thesteam cracking may be performed at a steam to hydrocarbon ratio rangingfrom a lower limit of any of 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, and0.6:1, by weight, to an upper limit of any of 0.5:1, 0.6:1, 0.7:1, and0.8:1, by weight, where any lower limit can be used with anymathematically-compatible upper limit. In particular embodiments, thesteam cracking in accordance with the present disclosure may beperformed at a steam to hydrocarbon ratio of approximately 0.6:1 byweight.

In one or more embodiments, the steam cracking in accordance with thepresent disclosure may be performed with a residence time of less than 1second. In some embodiments, the steam cracking may be performed with aresidence time ranging from a lower limit of any of 0.01, 0.10, 0.20,0.30, 0.35, and 0.40 seconds to an upper limit of any of 0.40, 0.50,0.60, 0.75, and 1.0 seconds, where any lower limit can be used with anymathematically-compatible upper limit. In particular embodiments, thesteam cracking in accordance with the present disclosure may beperformed with a residence time of approximately 0.35 seconds.

The steam cracking 210 of one or more embodiments may produce asteam-cracked product stream 22. The product stream 22 may comprise aportion of light (C₂₋₄) olefins. In some embodiments, the product streammay comprise light olefins in an amount of 30 wt. % or more, 40 wt. % ormore, or 50 wt. % or more. In some embodiments, the product stream maycomprise light olefins in an amount ranging from about 40 to 60 wt. %or, in particular embodiments, about 45 to 55 wt. %. In one or moreembodiments, the product stream 22 may comprise an aromatic portion thatmay include one or more of benzene, toluene, and xylenes. In someembodiments, the product stream may comprise an aromatic portion in anamount of 20 wt. % or less. In some embodiments, the product stream 22may comprise the aromatic portion in an amount ranging from about 5 to15 wt. %. The cracked product stream may be treated, recovered andfurther processed by any method, and for any use, known to one ofordinary skill in the art.

The iso-paraffin stream 20 may be treated, recovered and furtherprocessed by any method, and for any use, known to one of ordinary skillin the art. In some embodiments, finished gasoline may be produced byblending at least a portion of the iso-paraffin stream with othergasoline components, such as one or more of butanes, butenes, pentanes,naphtha, catalytic reformate, isomerate, alkylate, polymer, aromaticextract, heavy aromatics, gasoline from catalytic cracking,hydrocracking, thermal cracking, thermal reforming, steam pyrolysis andcoking, oxygenates such as methanol, ethanol, propanol, isopropanol,tert-butyl alcohol, sec-butyl alcohol, methyl tertiary butyl ether,ethyl tertiary butyl ether, methyl tertiary amyl ether and higheralcohols and ethers, and small amounts of additives to provide a desiredproperty.

FIG. 3 depicts a process and a system of one or more embodiments of thepresent disclosure, the system comprising a separation unit 200 and anisomerization unit 220. It is noted that component 200 and feeds 10, 20,and 21 are the same as discussed above with regard to FIG. 2 and, thoughtheir description is not repeated, each stream, component, and conditiondescribed above is also present in the embodiment shown in FIG. 3

Generally, the processes represented by FIG. 3 differ from thoserepresented by FIG. 2, discussed above, in that the normal paraffinstream 21 is fed to an isomerization unit 220 where it is isomerized,rather than the steam cracking unit 210 of FIG. 2.

In one or more embodiments, an isomerization in accordance with thepresent disclosure will increase the RON of the hydrocarbon mixture, andcomprises mixing the normal paraffin stream 21 with an excess ofhydrogen gas (not shown in FIG. 3) to dissolve a portion of the hydrogengas in the liquid hydrocarbon feedstock to produce a hydrogen-enrichedliquid hydrocarbon feedstock and reacting the normal paraffins toproduce isomerates. The normal paraffin stream 21 of one or moreembodiments may have a RON of 60 or less, of 50 or less, or of 45 orless.

The isomerization unit may have any suitable configuration known to oneof ordinary skill in the art. In some embodiments, the unit can includeone or more fixed-bed, moving-bed, fluidized-bed, or batch reactorsystems. The isomerization reaction zone may include a single reactor ormultiple reactor configurations with suitable fluid communicationbetween reactors and thermal means and control to ensure that thedesired isomerization temperature is maintained at the inlet to eachzone.

In one or more embodiments, the isomerization may use any suitablecatalyst known to a person of ordinary skill in the art. Theisomerization catalysts of one or more embodiments may include, but arenot limited to, those that are amorphous, for example comprisingamorphous alumina, or zeolitic, such as platinum on alumina, a zeolite,a chlorinated alumina, a sulfated zirconia and platinum, a platinumgroup metal on chlorided alumina, a tungstated support of a Group IVBoxide or hydroxide. In one or more embodiments the catalyst may comprise0.05 wt. % to 5 wt. % of a Group VIIIB metal. In some embodiments, thecatalyst may comprise a base material, such as zeolite or alumina, andone or more Group IIIB or IVB metal oxides. In particular embodiments,the catalyst may be a zirconia-based catalyst. As used herein, the term“zeolite” includes not only aluminosilicates but variants in which thealuminum is replaced by other trivalent elements and/or silicon isreplaced by other tetravalent elements.

In one or more embodiments, the isomerization in accordance with thepresent disclosure may be performed at a pressure ranging from about 10to 100 bar. In some embodiments, the isomerization may be performed at apressure ranging from a lower limit of any of 10, 20, 30, 35, 40, and 50bar to an upper limit of any of 45, 50, 60, 70, 80, 90, and 100 bar,where any lower limit can be used with any mathematically-compatibleupper limit. In particular embodiments, the isomerization in accordancewith the present disclosure may be performed at a pressure ofapproximately 40 bar.

In one or more embodiments, the isomerization in accordance with thepresent disclosure may be performed at a hydrogen to hydrocarbon moleratio (H₂:HC) ranging from about 0.01:1 to 20:1. In some embodiments,the isomerization may be performed at a H₂:HC ranging from a lower limitof any of 0.01:1, 0.02:1, 0.03:1, 0.04:1, 0.05:1, and 0.10:1, to anupper limit of any of 0.06:1, 0.08:1, 0.10:1, 0.20:1, 0.50:1, 1:1, 5:1,10:1, and 20:1, where any lower limit can be used with anymathematically-compatible upper limit. In particular embodiments, thesteam cracking in accordance with the present disclosure may beperformed at a H₂:HC of approximately 0.05:1.

In one or more embodiments, the isomerization may be performed with aliquid hourly space velocity (LHSV) ranging from a lower limit of any of0.2, 0.5, 1.0, and 1.5 h⁻¹ to an upper limit of any of 1.5, 2.0, 5.0,and 20 h⁻¹, where any lower limit can be used with anymathematically-compatible upper limit. In particular embodiments, theisomerization in accordance with the present disclosure may be performedwith a LHSV of approximately 1.5 h⁻¹.

In one or more embodiments, the isomerization in accordance with thepresent disclosure may be performed at a temperature ranging from about20 to 300° C. In some embodiments, the isomerization may be performed ata temperature ranging from a lower limit of any of 20, 50, 80, 100, 120,140, 160, and 180° C. to an upper limit of any of 180, 200, 220, 240,260, and 300° C., where any lower limit can be used with anymathematically-compatible upper limit. In particular embodiments, theisomerization in accordance with the present disclosure may be performedat a temperature of approximately 160° C. In some embodiments, lowerreaction temperatures may be preferred to favor equilibrium mixtureshaving the highest concentration of high-octane highly branchediso-paraffins and to minimize cracking of the feed to lighterhydrocarbons. One of ordinary skill in the art would appreciate, withthe benefit of this disclosure, that the temperature and otherconditions are also partially determined by the type of catalyst used.

In some embodiments, the isomerization conditions in the isomerizationmay be maintained at levels effective to maintain at least about 90% byvolume of the normal paraffin stream 21 in liquid phase. In particularembodiments, the isomerization is performed under conditions effectiveto increase the RON of the normal paraffin stream 21. In someembodiments, the resulting iso-paraffin stream 24 may have a RON of 75or more, of 80 or more, of 85 or more, or of 90 or more. Theiso-paraffin stream 24 of one or more embodiments may comprise asignificant isomerate portion. In some embodiments, the resultingiso-paraffin stream 24 may comprise isomerates in an amount of 80 wt. %or more, 90 wt. % or more, 95 wt. % or more, or 99 wt. % or more. Insome embodiments, the iso-paraffin stream may consist essentially of, orin other embodiments consist of, isomerates.

The iso-paraffin stream 24 may be treated, recovered and furtherprocessed by any method, and for any use, known to one of ordinary skillin the art. The stream 24 may be treated the same as, or different from,stream 20. In one or more embodiments, the stream 24 may be combined 25with the iso-paraffin stream 20. In some embodiments, finished gasolinemay be produced by blending at least a portion of the iso-paraffinstream 24 with other gasoline components, such as one or more ofbutanes, butenes, pentanes, naphtha, catalytic reformate, isomerate,alkylate, polymer, aromatic extract, heavy aromatics, gasoline fromcatalytic cracking, hydrocracking, thermal cracking, thermal reforming,steam pyrolysis and coking, oxygenates such as methanol, ethanol,propanol, isopropanol, tert-butyl alcohol, sec-butyl alcohol, methyltertiary butyl ether, ethyl tertiary butyl ether, methyl tertiary amylether and higher alcohols and ethers, and small amounts of additives toprovide a desired property.

FIG. 4 depicts a process and a system of one or more embodiments of thepresent disclosure, the system comprising a separation unit 200 and anaromatization unit 230. It is noted that component 200 and feeds 10, 20,and 21 are the same as discussed above with regard to FIGS. 2 and 3 and,though their description is not repeated, each stream, component, andcondition described above is also present in the embodiment shown inFIG. 4.

Generally, the processes represented by FIG. 4 differ from thoserepresented by FIGS. 2 and 3, discussed above, in that the normalparaffin stream 21 is fed to an aromatization unit 230 where it isaromatized, rather than the steam cracking unit 210 of FIG. 2 or theisomerization unit 220 of FIG. 3.

In one or more embodiments, the aromatization of the present disclosuremay be any such process known to one of ordinary skill in the art thatis suitable for converting normal paraffins into a product stream richin one or more of benzene, toluene and xylenes, and light hydrocarbongases. Benzene and xylenes are useful petrochemical building blocks formany chemical and polymer materials. In one or more embodiments, thearomatization 230 generates an aromatic-rich stream 26.

In one or more embodiments, the aromatization in accordance with thepresent disclosure may be performed at a pressure ranging from about 0.5to 80 bar. In some embodiments, the aromatization may be performed at apressure ranging from a lower limit of any of 0.5, 0.8, 1.0, 1.5, 5, 10,and 20 bar to an upper limit of any of 1.2, 1.5, 2, 5, 10, 25, 50, and80 bar, where any lower limit can be used with anymathematically-compatible upper limit. In particular embodiments, thearomatization in accordance with the present disclosure may be performedat a pressure of approximately 1 bar.

In one or more embodiments, the aromatization may be performed with aliquid hourly space velocity (LHSV) ranging from a lower limit of any of0.2, 0.5, 1.0, and 1.5 h⁻¹ to an upper limit of any of 1.5, 2.0, 5.0,and 20 h⁻¹, where any lower limit can be used with anymathematically-compatible upper limit. In particular embodiments, thearomatization in accordance with the present disclosure may be performedwith a LHSV of approximately 1 h⁻¹.

In one or more embodiments, the aromatization may be performed with anysuitable aromatization catalyst known to one of ordinary skill in theart. In some embodiments, the catalyst may be a zeolite. In particularembodiments a MFI type zeolite catalyst may be used. The catalyst of oneor more embodiments may be used in either a moving bed or a fixed bed.

In one or more embodiments, the aromatization in accordance with thepresent disclosure may be performed at a temperature ranging from about200 to 700° C. bar. In some embodiments, the aromatization may beperformed at a temperature ranging from a lower limit of any of 200,300, 400, 500, and 550 C to an upper limit of any of 500, 550, 600, and700° C., where any lower limit can be used with anymathematically-compatible upper limit. In particular embodiments, thearomatization in accordance with the present disclosure may be performedat a temperature of approximately 550° C.

The aromatization of one or more embodiments may generate anaromatic-rich stream 26, which comprises a portion of one or more ofbenzene, toluene, xylenes. In some embodiments, the aromatic-rich stream26 may comprise benzene in an amount ranging from about 5 to 10 wt. %.In some embodiments, the aromatic-rich stream 26 may comprise xylenes inan amount ranging from about 5 to 10 wt. %. In some embodiments, thearomatic-rich stream 26 may comprise no substantial quantity of toluene.In one or more embodiments, the aromatic-rich stream 26 comprises anaromatics content of 10 wt. % or more, 15 wt. % or more, 20 wt. % ormore, or 25 wt. % or more. In some embodiments, the aromatic-rich stream26 comprises an aromatics content of 80 wt. % less, 60 wt. % or less, 40wt. % or more, or 20 wt. % or less. In one or more embodiments, thearomatic-rich stream 26 is passed downstream for additional processingand separations, including petrochemical processing. The aromatics-richsteam 26 of one or more embodiments may comprise an unreacted portion ofthe normal paraffins of stream 21. The unreacted paraffins mayconstitute the aromatics-rich steam 26 in an amount of 30 wt. % or less,20 wt. % or less, or 10 wt. % or less. The aromatics-rich steam 26 ofone or more embodiments may further comprise a portion of light (C₂₋₄)olefins and, in some embodiments, be combined 27 with the iso-paraffinstream 20.

FIG. 5 depicts a process and a system of one or more embodiments of thepresent disclosure, the system comprising a separation unit 200, anaromatization unit 230, and a cracking unit 310. It is noted thatcomponents 200 and 230, and feeds 10, 20, and 21 are the same asdiscussed above with regard to FIGS. 2-4 and, though their descriptionis not repeated, each stream, component, and condition described aboveis also present in the embodiment shown in FIG. 3.

Generally, the processes represented by FIG. 5 differ from thoserepresented by

FIG. 4, discussed above, in that the aromatization unit 230 provides twostreams: an aromatic stream 36 and a non-aromatic stream 39, which issubsequently subjected to steam cracking 310, rather than thearomatization of FIG. 4 that provides only one aromatic-rich stream.

In one or more embodiments, the aromatization 230 of the normal paraffinstream 21 produces a variety of hydrocarbon components. Such componentscomprise one or more aromatics, including one or more of the groupconsisting of benzene, toluene and xylene. The aromatization of someembodiments further provides one or more of an unreacted portion of thenormal paraffins of stream 21, an isomerate portion, and a portion oflight (C₂₋₄) olefins. In some embodiments, the aromatics may beseparated and removed from the aromatization unit 230 as an aromaticstream 36. The aromatics may be separated from the other components byany method known to the art, including fractionation. The remainingproducts of aromatization are sent as a non-aromatic stream 39 to asteam cracking unit 310.

The aromatic stream 36 of one or more embodiments may consistessentially of one or more of benzene, toluene, and xylenes. In someembodiments, the aromatic stream 36 may consist of a mixture of one ormore of benzene, toluene, and xylenes. In some embodiments, the aromaticstream 36 comprises benzene in an amount ranging from 40 to 60 wt. %. Insome embodiments, the aromatic stream 36 comprises xylenes in an amountranging from 40 to 60 wt. %.

The non-aromatic stream 39 may comprise an unreacted portion of thenormal paraffins of stream 21. The non-aromatic stream may compriseunreacted paraffins in an amount of 30 wt. % or less, 20 wt. % or less,or 10 wt. % or less. The non-aromatic stream 39 may comprise anisomerate portion, which in some embodiments may constitute thenon-aromatic stream 39 in an amount of 30 wt. % or less, 20 wt. % orless, or 10 wt. % or less. The non-aromatic stream 39 of one or moreembodiments may further comprise a portion of light (C₂₋₄) olefins.

In one or more embodiments, the non-aromatic stream 39 may be steamcracked. The steam-cracking 310 may be performed in accordance with anyof the conditions and configurations discussed previously regarding thesteam cracking 210 of FIG. 2. The steam cracking generates an olefinicstream 32. The olefinic stream 39 may comprise a significant portion ofethylene in addition to other light olefins and aromatics. The olefinicstream 39 may be treated by any method known by one of ordinary skill inthe art, and passed downstream for additional processing andseparations, including petrochemical processing.

EXAMPLES

The following examples are merely illustrative and should not beinterpreted as limiting the scope of the present disclosure.

To illustrate the effect of separation on the product compositionprovided by some of the aforementioned embodiments, Comparative Examples1 and 2 and Examples 1-4 are given below. Reported in Tables 1-6 are thematerial balances (by mass) for each Example, as obtained by simulations(Examples 1 and 4 and Comp. Ex 1-2) and experiments (Examples 2-3).

Example 1 was prepared by a process in accordance with one or moreembodiments represented by FIG. 2, involving a paraffin separation stepand subsequent steam cracking of a normal paraffin stream. Theseparation was performed at a pressure of 1-3 bars, with a proprietarymolsieve 5 A adsorbent, and at a temperature of 100-260° C. The steamcracking was performed at a temperature of 800° C., a pressure of 1 bar,a steam-to-hydrocarbon weight ratio of 0.6:1, and a residence time of0.35 seconds.

TABLE 1 Material Balance for Example 1 (streams labelled as per FIG. 2)Stream# 10 21 20 22 Light Naphtha 80,000 Isomerate 38,640 Paraffins41,360 Hydrogen 620 Methane 7,114 Ethane Ethylene 13,897 PropanePropylene 6,452 Butadiene 1,861 Other C4 1,737 Benzene 2,771 Toluene1,406 Xylenes Pyrolysis 3,557 Gasoline Fuel oil 1,944 Total 80,00041,360 38,640 41,360 RON 62.3 43.1 82.8 NA

Example 2 was prepared by a process in accordance with one or moreembodiments represented by FIG. 3, involving a paraffin separation stepand subsequent isomerization of a normal paraffin stream. The separationwas performed as for Example 1. The isomerization was performed at atemperature of 160° C., an outlet pressure of 40 bar, a H₂:hydrocarbonmole ratio of 0.05:1, a LHSV of 1.5 h⁻¹, and with a zirconia commercialcatalyst.

TABLE 2 Material Balance for Example 2 (streams labelled as per FIG. 3)Stream# 10 21 20 24 25 Light Naphtha 80,000 Isomerate 38,640 40,94679,586 Paraffins 41,360 — Hydrogen — Methane — Ethane Ethylene — PropanePropylene — Butadiene — Other C4 — Benzene — Toluene — Xylenes Pyrolysis— Gasoline Fuel oil — Total 80,000 41,360 38,640 — 79,586 RON 62.3 43.182.8 NA 82.8

Example 3 was prepared by a process in accordance with one or moreembodiments represented by FIG. 4, involving a paraffin separation stepand subsequent aromatization of a normal paraffin stream. The separationwas performed as for Example 1. The aromatization was performed at atemperature of 550° C., an outlet pressure of 1 bar, a LHSV of 1 h⁻¹,and with a MFI-type zeolite catalyst.

TABLE 3 Material Balance for Example 3 (streams labelled as per FIG. 4)Stream# 10 21 20 26 27 Light Naphtha 80,000 Isomerate 38,640 7,60746,247 Paraffins 41,360 8,577 8,577 Hydrogen — Methane 1,386 1,386Ethane 3,344 3,344 Ethylene 2,179 2,179 Propane 5,923 5,923 Propylene2,447 2,447 Butadiene — Other C4 3,771 3,771 Benzene 3,082 3,082 Toluene— Xylenes 3,044 3,044 Pyrolysis — Gasoline Fuel oil — Total 80,00041,360 38,640 41,360 80,000 RON 62.3 43.1 82.8 NA 82.8

Example 4 was prepared by a process in accordance with one or moreembodiments represented by FIG. 5, involving a paraffin separation stepand subsequent aromatization of a normal paraffin stream. Thearomatization gives a non-aromatic stream that is then steam cracked.The separation, aromatization, and steam cracking were performed as forExamples 1-3.

TABLE 4 Material Balance for Example 4 (streams labelled as per FIG. 5)Stream# 10 21 20 39 36 32 Light Naphtha 80,000 Isomerate 38,640 7,607Paraffins 41,360 8,577 Hydrogen 768.0 Methane 1,386 7311.6 Ethane 3,3440.0 Ethylene 2,179 12896.3 Propane 5,923 0.0 Propylene 2,447 4637.9Butadiene 1176.8 Other C4 3,771 1182.9 Benzene 3,082 1440.2 Toluene630.6 Xylenes 3,044 291.3 Pyrolysis Gasoline 1508.9 Fuel oil 760.6 Total80,000 41,360 38,640 35,233 6,127 32,605 RON 62.3 43.1 82.8 82.8 NA NA

Comparative Example 1 was prepared by a process in accordance with oneor more embodiments represented by FIG. 1A, involving steam cracking alight naphtha feed. The steam cracking was performed as for Example 1.

TABLE 5 Material Balance for Comp. Example 1 (streams labelled as perFIG. 1A) Stream# 10 12 Light Naphtha 80,000 Isomerate Paraffins Hydrogen1,200 Methane 13,760 Ethane — Ethane 26,880 Propane — Propylene 12,480Butadiene 3,600 Other C4 3,360 Benzene 5,360 Toluene 2,720 XylenesPyrolysis Gasoline 6,880 Fuel oil 3,760 Total 80,000 80,000 RON 62.28 NA

Comparative Example 2 was prepared by a process in accordance with oneor more embodiments represented by FIG. 1B, involving isomerizing alight naphtha feed. The isomerization was performed as for Example 2.

TABLE 6 Material Balance for Comp. Example 2 (streams labelled as perFIG. 1B) Stream# 10 14 Light Naphtha 80,000 Isomerate 79,897 ParaffinsHydrogen Methane Ethane Ethylene Propane Propylene Butadiene Other C4Benzene Toluene Xylenes Pyrolysis Gasoline Fuel oil Total 80,000 79,897RON 62.3 82.0

Although the preceding description has been described herein withreference to particular means, materials and embodiments, it is notintended to be limited to the particulars disclosed herein; rather, itextends to all functionally equivalent structures, methods and uses,such as are within the scope of the appended claims. In the claims,means-plus-function clauses are intended to cover the structuresdescribed herein as performing the recited function and not onlystructural equivalents, but also equivalent structures. Thus, although anail and a screw may not be structural equivalents in that a nailemploys a cylindrical surface to secure wooden parts together, whereas ascrew employs a helical surface, in the environment of fastening woodenparts, a nail and a screw may be equivalent structures. It is theexpress intention of the applicant not to invoke 35 U.S.C. § 112(f) forany limitations of any of the claims herein, except for those in whichthe claim expressly uses the words ‘means for’ together with anassociated function.

1. A process for treatment of a light naphtha feedstock, the processcomprising: separating the light naphtha feedstock consisting of normalparaffins and iso-paraffins having 5 and 6 carbon atoms into aniso-paraffin stream and a normal paraffin stream consisting of 5 and 6carbon atoms; aromatizing the normal paraffin stream to produce anaromatic stream and a non-aromatic stream; and steam cracking thenon-aromatic stream to provide an olefinic stream.
 2. (canceled)
 3. Theprocess of claim 1, wherein the iso-paraffin stream is sent to agasoline pool.
 4. The process of claim 1, wherein the separating isperformed with 5 A molecular sieves.
 5. The process of claim 1, whereinthe separating is performed at a pressure ranging from about 1-3 bar. 6.The process of claim 1, wherein the separating is performed at atemperature ranging from 100-260° C.
 7. The process of claim 1, whereinthe aromatizing is performed with a MFI zeolite catalyst.
 8. The processof claim 1, wherein the aromatizing is performed at a temperature of500-600° C.
 9. The process of claim 1, wherein the steam cracking isperformed at a temperature of 750-850° C.
 10. The process of claim 1,wherein the steam cracking is performed with a steam-to-hydrocarbonratio ranging from 0.5:1 to 0.7:1 by weight.
 11. A process for treatmentof a light naphtha feedstock, the process comprising: separating thefeedstock consisting of normal paraffins and iso-paraffins having 5 and6 carbon atoms into a first iso-paraffin stream and a normal paraffinstream consisting of 5 and 6 carbon atoms with 5 A molecular sieves at apressure of about 1-3 bars and a temperature of 100-260° C.; and atleast one of steam cracking, isomerizing, and aromatizing the normalparaffin stream to produce a product stream.
 12. (canceled)
 13. Theprocess of claim 11, wherein the first iso-paraffin stream is sent to agasoline pool.
 14. The process of claim 11, wherein the processcomprises the steam cracking, and wherein the steam cracking isperformed with a steam-to-hydrocarbon ratio ranging from 0.5:1 to 0.7:1by weight.
 15. The process of claim 11, wherein the process comprisesthe steam cracking, and wherein the steam cracking is performed at atemperature of 750-850° C.
 16. The process of claim 11, wherein theprocess comprises the isomerizing, and wherein the isomerizing comprisesmixing the normal paraffin stream with an amount of hydrogen such that amolar ratio of hydrogen to the normal paraffin stream is of the range0.04:1 to 0.06:1.
 17. The process of claim 11, wherein the processcomprises the isomerizing, and wherein the isomerizing is performed at atemperature ranging from about 100 to 200° C.
 18. The process of claim11, wherein the process comprises the isomerizing, and wherein theisomerizing is performed with a zirconia-containing catalyst.
 19. Theprocess of claim 11, wherein the process comprises the isomerizing, andwherein the isomerizing is performed with a liquid hourly space velocityranging from 1.0 to 2.0 h⁻¹.
 20. The process of claim 11, wherein theprocess comprises the aromatizing, and wherein the aromatizing isperformed at a temperature of 500-600° C.